The availability of metamaterials with properties that can be actively tuned is crucial for the future development of various metamaterial-based technologies. Here we show that by using silver nanoparticles equipped with a thermally responsive organic coating a metamaterial is obtained with reversibly switchable properties. The material investigated exhibits dynamic self-assembly resulting from temperature-dependent changes of organic coating shape, which translates to a switchable spatial distribution of the silver nanoparticles. This in turn strongly influences the optical properties of the entire material. The measured optical characteristics of the material are in excellent agreement with theoretical calculations, which allow us to use the latter to predict a dynamically tunable epsilon-near-zero behaviour of the metamaterial. The suggested methodology opens new routes for tunable metamaterials that operate in the visible region and will enable various applications for soft-matter-based optical devices.

Spontaneous formation of smectic and columnar structures was observed when spherical gold nanoparticles were functionalized with mesogenic thiols (see layered structure and X-ray pattern of a sample in smectic phase). The particle ordering is stimulated by softening of the interparticle potential and flexibility for deformation of the grafting layer.

The availability of helical assemblies of plasmonic nanoparticles with precisely controlled and tunable structures can play a key role in the future development of chiral plasmonics and metamaterials. Here, a strategy to efficiently yield helical structures based on the cooperative interactions of liquid crystals and gold nanoparticles in thin films is developed. These nanocomposites exhibit exceptional long‐range hierarchical order across length scales, which results from the growth mechanism of nanoparticle‐coated twisted nanoribbons and their ability to form organized bundles. The helical assembly formation is governed by the presence of rationally functionalized nanoparticles. Importantly, the thickness of the achieved nanocomposites can be reversibly reconfigured owing to the polymorphic nature of the liquid crystal. The versatility of the proposed approach is demonstrated by preparing helices assembled from nanoparticles of different geometries and dimensions (spherical and rod‐like). The described strategy may become an enabling technology for structuring nanoparticle assemblies with high precision and fabricating optically active materials.

On the GO: The basal plane allylic alcohol functionality of graphite oxide (GO) can be converted into N,N‐dimethylamide groups through an Eschenmoser–Claisen sigmatropic rearrangement by using N,N‐dimethylacetamide dimethyl acetal. Subsequent saponification of these groups affords the carboxylic acids (see picture), which, when deprotonated, electrostatically stabilize the graphene sheets in an aqueous environment.

Nanoparticle ordered aggregates are promising candidates for future application in a variety of sensing, optical and electronic technologies, mainly based on collective interactions between individual nano-building blocks. Physicochemical properties of such assemblies depend on nanoparticle spacing, therefore a lot of effort throughout the last years was put on development of assembly methods allowing control over aggregates structure. In this minireview we describe efficient self-assembly process based on the utilization of liquid-crystalline ligands grafted onto nanoparticle surface. We show strategies used to synthesize liquid-crystalline nanoparticles as well as discuss parameters influencing structural and thermal characteristic of aggregates. It is also demonstrated that the liquid-crystalline approach offers access to dynamic self-assembly and metamaterials with anisotropic plasmonic properties, which makes this strategy unique among others.

BackgroundFeline injection-site sarcomas are malignant skin tumors of mesenchymal origin, the treatment of which is a challenge for veterinary practitioners. Methods of treatment include radical surgery, radiotherapy and chemotherapy. The most commonly used cytostatic drugs are cyclophosphamide, doxorubicin and vincristine. However, the use of cytostatics as adjunctive treatment is limited due to their adverse side-effects, low biodistribution after intravenous administration and multidrug resistance. Colloid gold nanoparticles are promising drug delivery systems to overcome multidrug resistance, which is a main cause of ineffective chemotherapy treatment. The use of colloid gold nanoparticles as building blocks for drug delivery systems is preferred due to ease of surface functionalization with various molecules, chemical stability and their low toxicity.MethodsStability and structure of the glutathione-stabilized gold nanoparticles non-covalently modified with doxorubicin (Au-GSH-Dox) was confirmed using XPS, TEM, FT-IR, SAXRD and SAXS analyses. MTT assay, Annexin V and Propidium Iodide Apoptosis assay and Rhodamine 123 and Verapamil assay were performed on 4 feline fibrosarcoma cell lines (FFS1WAW, FFS1, FFS3, FFS5). Statistical analyses were performed using Graph Pad Prism 5.0 (USA).ResultsA novel approach, glutathione-stabilized gold nanoparticles (4.3 +/- 1.1 nm in diameter) non-covalently modified with doxorubicin (Au-GSH-Dox) was designed and synthesized. A higher cytotoxic effect (p<0.01) of Au-GSH-Dox than that of free doxorubicin has been observed in 3 (FFS1, FFS3, FFS1WAW) out of 4 feline fibrosarcoma cell lines. The effect has been correlated to the activity of glycoprotein P (main efflux pump responsible for multidrug resistance).ConclusionsThe results indicate that Au-GSH-Dox may be a potent new therapeutic agent to increase the efficacy of the drug by overcoming the resistance to doxorubicin in feline fibrosarcoma cell lines. Moreover, as doxorubicin is non-covalently attached to glutathione coated nanoparticles the synthesized system is potentially suitable to a wealth of different drug molecules.

Mirror symmetry breaking in materials is a fascinating phenomenon that has practical implications for various optoelectronic technologies. Chiral plasmonic materials are particularly appealing due to their strong and specific interactions with light. In this work we broaden the portfolio of available strategies toward the preparation of chiral plasmonic assemblies, by applying the principles of chirality synchronization—a phenomenon known for small molecules, which results in the formation of chiral domains from transiently chiral molecules. We report the controlled cocrystallization of 23 nm gold nanoparticles and liquid crystal molecules yielding domains made of highly ordered, helical nanofibers, preferentially twisted to the right or to the left within each domain. We confirmed that such micrometer sized domains exhibit strong, far-field circular dichroism (CD) signals, even though the bulk material is racemic. We further highlight the potential of the proposed approach to realize chiral plasmonic thin films by using a mechanical chirality discrimination method. Toward this end, we developed a rapid CD imaging technique based on the use of polarized light optical microscopy (POM), which enabled probing the CD signal with micrometer-scale resolution, despite of linear dichroism and birefringence in the sample. The developed methodology allows us to extend intrinsically local effects of chiral synchronization to the macroscopic scale, thereby broadening the available tools for chirality manipulation in chiral plasmonic systems.

Composite structures exhibiting a periodic arrangement of building blocks can be found in natural systems at different length scales. Recreating such systems in artificial composites using the principles of self-assembly has been a great challenge, especially for 1D microscale systems. Here, we present a purposely designed composite material consisting of gold nanoparticles and a nematic liquid crystal matrix that has the ability to self-create a periodic structure in the form of a one-dimensional photonic lattice through a phase separation process occurring in a confined space. Our strategy is based on the use of a thermoswitchable medium that reversibly and quickly responds to both heating and cooling. We find that the period of the structure is strongly related to the size of the confining space. We believe that our findings will allow us to not only better understand the phase separation process in multicomponent soft/colloid mixtures with useful optical properties but also improve our understanding of the precise assembly of advanced materials into one-dimensional periodic systems, with prospective applications in future photonic technologies.